Process for converting one or more C3-C12 oxygenates

ABSTRACT

A process for converting one or more C3-C12 oxygenates comprising oxygenates comprising: contacting a feed, which feed comprises one or more C3-C12 oxygenates, with hydrogen at a hydrogen partial pressure of more than 1.0 Mega Pascal in the presence of a sulphided carbon-carbon coupling catalyst; wherein the carbon-carbon coupling catalyst comprises equal to or more than 60 wt % of a zeolite and in the range from equal to or more than 0.1 wt % to equal to or less than 10 wt % of a hydrogenation metal, based on the total weight of the carbon-carbon coupling catalyst; and wherein the zeolite comprises 10-membered and/or 12-membered ring channels and a Silica to Alumina molar Ratio (SAR) in the range from equal to or more than 10 to equal to or less than 300.

PRIORITY CLAIM

The present application is the National Stage (§ 371) of InternationalApplication No. PCT/EP2013/077545, filed Dec. 19, 2013, which claimspriority from Indian Patent Application No. 5514/CHE/2012, filed Dec.31, 2012 incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to a process for converting one or more C3-C12oxygenates. Further this invention relates to a process for converting afeed containing one or more C3-C12 oxygenates to a middle distillateboiling product.

BACKGROUND OF THE INVENTION

With increasing demand for liquid transportation fuels, decreasingreserves of ‘easy oil’ (crude petroleum oil that can be accessed andrecovered easily) and increasing constraints on carbon footprints ofsuch fuels, it is becoming increasingly important to develop routes toproduce liquid transportation fuels from biomass in an efficient manner.Such liquid transportation fuels produced from biomass are sometimesalso referred to as biofuels. Biomass offers a source of renewablecarbon. Therefore, when using such biofuels, it may be possible toachieve more sustainable CO₂ emissions over petroleum-derived fuels.

WO2010/053681 describes a biofuel production process comprising amongstothers converting biomass to alcohol, and synthesizing a liquidhydrocarbon fuel from the alcohol. WO2010/053681 describes severalprocesses for converting the biomass to alcohol. WO2010/053681 furthermentions that alcohols may be directly oligomerized to hydrocarbonsapparently in the absence of hydrogen at high temperatures (300-450° C.)and moderate pressures (1-40 atm.) in the presence of a zeolite catalystin an oligomerization reactor (see also FIG. 10 of WO2010/053681). It isfurther indicated that by controlling the temperature and pressure ofthe oligomerization process and/or the composition of the zeolite, it ispossible to direct the production of longer or shorter chainhydrocarbons. WO2010/053681 further mentions that it is also possible tocontrol the amount of alkane branching in the final product. In itsexample 1, 27 tonnes of secondary alcohols are oligomerized at 350° C.at 10 atm. in the presence of zeolite catalyst and oxygen to produce 17tonnes of gasoline and water. The alcohol to gasoline conversionapparently involves also a hydrogenation step. The approximate yield ofgasoline based on weight of alcohol feed may be calculated to beapproximately 63 wt %.

In its example 5, 27 tonnes of mixed ketones are converted toapproximately 28 tonnes of secondary alcohols by hydrogenation over anickel catalyst at approximately 130° C. and 15 atm hydrogen. The 28tonnes of secondary alcohols are oligomerized at 350° C. at 10 atm. inthe presence of zeolite catalyst to produce 12 tonnes of gasoline, 5tonnes of light hydrocarbon residuals and 20 tonnes of water. Theapproximate yield of gasoline based on weight of alcohol feed may becalculated to be approximately 42 wt %.

In his thesis titled “TRANSFORMATION OF ACETONE AND ISOPROPANOL TOHYDROCARBONS USING HZSM-5 CATALYST”, obtainable from the Office ofGraduate Studies of the Texas A&M University, USA, (December 2009), S.T. Vasquez describes a transformation of acetone and isopropanol tohydrocarbons using a HZSM-5 catalyst. The thesis describes that zeolitesolid-acid catalyst HZSM-5 can transform either alcohols or ketones intohydrocarbons. Catalysts having a Silica to Alumina molar Ratio (SAR) of80 and 280 were used. Vasquez suggests for further studies to modify thecatalyst HZSM-5 with metals such as Nickel or Copper.

In the processes of WO2010/053681 and Vasquez deactivation of the priorart catalysts may become an issue when the prior art processes would beapplied on a commercial scale in a continuous manner. Without wishing tobe bound by any kind of theory it is believed that operating the priorart processes for longer operating times may lead to excessive cokingand subsequent deactivation of the catalysts.

For example Gayubo et al. in their article titled “Transformation ofOxygenate components of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. I.Alcohols and Phenols”, published in Ind. Eng. Chem. Res. 2004, vol 43,page 2610 to 2618 and their article titled “Transformation of OxygenateComponents of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. II. Aldehydes,Ketones, and Acids” published in Ind. Eng. Chem. Res. 2004, 43,2619-2626 describe the effects of temperature and space time on thetransformation over a HZSM-5 zeolite catalyst of several modelcomponents of the liquid product obtained by the flash pyrolysis ofvegetable biomass (1-propanol, 2-propanol, 1-butanol, 2-butanol, phenoland 2-methoxyphenol). The HZSM-5 zeolite catalyst comprised 30 wt %bentonite, 45 wt % fused alumina and 25 wt % of a HZSM-5 zeolite havinga Silica to Alumina molar Ratio of 24. They explain that the viabilityof transforming oxygenates into hydrocarbons was found to be limited bythe catalyst deactivation by coke, and that this deactivation effectsthe product distribution with time on stream.

It would be an advancement in the art to provide a process forconversion of a feed containing one or more C3-C12 oxygenate(s), whichprocess can be operated for a prolonged period of time withoutsubstantial deactivation of the catalyst.

SUMMARY OF THE INVENTION

It has now been advantageously found that a feed containing one or moreC3-C12 oxygenate(s) can be converted to a so-called middle distillateboiling product in a process operated for a prolonged period of timewithout substantial deactivation of the catalyst by using a specificcatalyst in combination with a high hydrogen pressure.

Accordingly the present invention provides a process for converting oneor more C3-C12 oxygenates comprising:

contacting a feed, which feed comprises one or more C3-C12 oxygenates,with hydrogen at a hydrogen partial pressure of more than 1.0 MegaPascalin the presence of a sulphided carbon-carbon coupling catalyst;

wherein the carbon-carbon coupling catalyst comprises equal to or morethan 60 wt % of a zeolite and in the range from equal to or more than0.1% wt to equal to or less than 10 wt % of a hydrogenation metal, basedon the total weight of the carbon-carbon coupling catalyst; and

wherein the zeolite comprises 10-membered and/or 12-membered ringchannels and a Silica to Alumina molar Ratio (SAR) in the range fromequal to or more than 10 to equal to or less than 300.

By a 10-membered and/or 12-membered ring channel is herein preferablyunderstood a ring channel comprising 10 respectively 12 tetrahedralatoms (such as silicon or aluminium atoms) in the ring.

It has now been found that such a process may advantageously allow foran extended catalyst stability against deactivation due to cokeformation and/or due to catalyst poisoning.

In addition, the process according to the invention may advantageouslyallow one to carry out the conversion in a single reactor or tworeactors in series allowing for a more efficient and cost-effectiveoperation.

Further such a process has been found suitable to produce a middledistillate boiling product. This middle distillate boiling product canbe obtained in good yields and may advantageously be used in theproduction of biofuels and/or biochemicals. By a middle distillateboiling product is herein preferably understood a product having aboiling point at 0.1 MegaPascal (MPa) in the range from equal to or morethan 140° C. to equal to or less than 370° C. as determined by ASTMmethod D2887. In addition, the process may advantageously allow one toconvert a feed containing two or more distinct C3-C12 oxygenates into amiddle distillate boiling product having a smooth distillation curve.

A still further advantage of the process of the invention may be thatthe process may allow one to vary the amount of aromatics in the productto fit the needs elsewhere in a refinery.

SUMMARY OF THE DRAWINGS

The invention is further illustrated by the following non-limitingdrawings:

FIG. 1 illustrates a first schematic example of a process according tothe invention.

FIG. 2 illustrates a second schematic example of a process according tothe invention.

FIG. 3 illustrates a third schematic example of a process according tothe invention.

FIG. 4 illustrates a fourth schematic example of a process according tothe invention.

FIG. 5 illustrates a boiling point distribution as determined by ASTMmethod D2887 of two products obtained by a process according to theinvention.

DETAILED DESCRIPTION OF THE INVENTION

In the process according to the invention a feed comprising one or moreC3-C12 oxygenates is converted.

In addition to the one or more C3-C12 oxygenates the feed may compriseone or more other components. Examples of such other components includeparaffinic, olefinic and/or aromatic hydrocarbon compounds.

The feed may also contain oxygenates other than the C3-C12 oxygenates,respectively other than the oxygenates as described in the belowpreferences. In a preferred embodiment, however, the feed containsessentially no oxygenates other than the C3-C12 oxygenates, respectivelyother than the oxygenates as described in the below preferences.

Preferably the feed comprises at least 50 wt %, more preferably at least70 wt % (weight percentage), and most preferably at least 90 wt % of oneor more C3-C12 oxygenates, based on the total weight of the feed. Thefeed may for example comprise in the range from equal to or more than 50wt % to equal to or less than 99.9 wt % or equal to or less than 99.8 wt% of the one or more C3-C12 oxygenates, based on the total weight of thefeed. More preferably the feed consists essentially of one or moreC3-C12 oxygenates and most preferably the feed consists of one or moreC3-C12 oxygenates. As described below, the feed may optionally be spikedwith an amount of sulphur in the range from equal to or more than 0.1 wt% to equal to or less than 0.2 wt %, based on the total weight of thefeed.

In the embodiments of this invention the one or more C3-C12 oxygenatesreferred to preferably consist of one or more C3-C10 oxygenates and morepreferably consist of one or more C3-C8 oxygenates.

By an oxygenate is herein understood a compound comprising at least oneor more carbon atoms, at least one or more hydrogen atoms and at leastone or more oxygen atoms. Examples of oxygenates include alkanols,ketones, aldehydes, carboxylic acids, ethers, esters and/or phenoliccompounds.

In this invention the one or more oxygenates referred to preferablyconsist of one or more aldehydes, one or more ketones, one or morealkanols and/or combinations thereof. For example the one or more C3-C12oxygenates are preferably oxygenates chosen from the group consisting ofone or more C3-C12 aldehydes, one or more C3-C12 ketones, one or moreC3-C12 alkanols and combinations thereof. More preferably the one ormore oxygenates herein referred to consist of one or more aldehydes, oneor more ketones and/or combinations thereof. Most preferably the one ormore oxygenates herein referred to consist of one or more ketones. Forexample, the one or more C3-C12 oxygenates referred to herein preferablyconsist of one or more C3-C12 ketones. The feed may therefore preferablybe a feed comprising at least 50 wt %, more preferably at least 70 wt %,and most preferably at least 90 wt % of one or more C3-C12 ketones; morepreferably a feed comprising at least 50 wt %, more preferably at least70 wt %, and most preferably at least 90 wt % of one or more C3-C10ketones; and most preferably a feed comprising at least 50 wt %, morepreferably at least 70 wt %, and most preferably at least 90 wt % of oneor more C3-C8 ketones.

By a “Cx”-oxygenate, -ketone, -aldehyde, -carboxylic acid, -ether,-ester or -alkanol is herein understood respectively an oxygenate,ketone, aldehyde, carboxylic acid, ether, ester or alkanol comprising xcarbon atoms. By a “Cx-Cy”-oxygenate, -ketone, -aldehyde, -carboxylicacid, -ether, -ester or -alkanol is herein understood respectively anoxygenate, ketone, aldehyde, carboxylic acid, ether, ester or alkanolcomprising in the range from equal to or more than “x” to equal to orless than “y” carbon atoms.

Examples of suitable alkanols include primary, secondary, linear,branched and/or cyclic alkanols, such as methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-butanol, pentanol, cyclopentanol, hexanol,cyclohexanol, 2-methyl-cyclopentanonol, heptanol, octanol, nonanol,decanol, undecanol, dodecanol, ethylene glycol, propylene glycol,1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol,octanediol, nonanediol, decanediol, undecanediol, dodecanediol, isomersthereof and/or mixtures thereof.

Examples of ketones include hydroxyketones, oxo-aldehydes, cyclicketones and/or diketones, such as acetone, propanone, 2-oxopropanal,butanone, butane-2,3-dione, 3-hydroxybutane-2-one, pentanone,cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, pentatrione,hexanone, hexane-2,3-dione, hexane-2,4-dione, hexane-2,5-dione,hexane-3,4-dione, hexane-triones, cyclohexanone,2-methyl-cyclopentanone, heptanones, octanones, nonanones, decanones,undecanones, dodecanones, 2-oxopropanal, 2-oxo-butanal, 3-oxo-butanal,isomers thereof and/or mixtures thereof.

Examples of aldehydes include acetaldehyde, propionaldehyde,butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal,undecanal, dodecanal, isomers thereof and/or mixtures thereof.

Examples of carboxylic acids include formic acid, acetic acid, propionicacid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid,isomers thereof, and/or mixtures thereof.

Any ethers are preferably ethers with alkyl groups containing in therange from 1 to 6 carbon atoms. Examples of ethers include dimethylether, diethyl ether, methyl ethyl ether, diphenyl ether, methyl phenylether, ethyl phenyl ether, and/or mixtures thereof.

Any esters are preferably esters of carboxylic acids containing in therange from 2 to 6 carbon atoms and alcohols containing in the range from1 to 4 carbon atoms. Examples of esters include methyl acetate, ethylacetate, methyl propanoate, ethyl propanoate, methyl butanoate, ethylbutanoate and/or mixtures thereof.

The process according to the invention is further especiallyadvantageous when the feed contains a plurality of two or more C3-C12oxygenates or more preferably when the feed contains a plurality ofthree or more C3-C12 oxygenates. It has advantageously been found thateven when a plurality of two or more distinctive C3-C12 oxygenates, ormore preferably a plurality of three or more distinctive C3-C12oxygenates, is fed to the process of the invention, still a middledistillate boiling product can be obtained that has a smooth boilingrange distribution. By two or more distinctive oxygenates is herein forexample understood two or more C3-C12 oxygenates comprising differentnumbers of carbon atoms.

The feed may be obtained from any source known to be suitable for thispurpose by the person skilled in the art.

Preferably the feed is derived from a biomass material. By a biomassmaterial is herein preferably understood a material which containsbio-based carbon atoms as determined in ASTM method D6866-10 titled“Standard Test Methods for Determining the Biobased Content of Solid,Liquid and Gaseous samples using Radiocarbon Analysis”. Examples of suchbiomass material include cellulosic material, lignocellulosic material,oils, fats and proteins. By a cellulosic material is herein preferablyunderstood a material containing cellulose, and optionally lignin and/orhemicellulose. By a lignocellulosic material is herein preferablyunderstood a material containing cellulose and lignin and optionallyhemicellulose.

In a preferred embodiment the feed may at least partly be derived from abiomass material by means of fermentation. Examples of suitablefermentation systems or bioreactors and methods therefore may includethose found in U.S. Pat. No. 5,962,307, U.S. Pat. No. 5,874,263 and U.S.Pat. No. 6,262,313, herein incorporated by reference.

Examples of suitable biomass materials include cellulose containingmunicipal wastes; food waste; agricultural wastes such as corn stover,soybean stover, corn cobs, rice straw, rice hulls, oat hulls, cornfibre, cereal straws such as wheat, barley, rye and oat straw; grasses;waste paper; sugar processing residues such as bagasse and beet pulp;and/or mixtures thereof.

In addition to the C3-C12 oxygenates the feed in the process accordingto the invention may contain in the range from equal to or more than 150to equal to or less than 2000 ppmw (parts per million by weight) sulphurand/or in the range from equal to or more than 300 to equal to or lessthan 5000 ppmw nitrogen. Such sulphur and/or nitrogen may suitablyoriginate from the biomass material, for example from proteins, fromwhich the feed may be derived.

In the process according to the invention, the feed is contacted withhydrogen in the presence of a sulphided carbon-carbon coupling catalyst.The carbon-carbon coupling catalyst comprises equal to or more than 60wt % of a zeolite and in the range from equal to or more than 0.1% wt toequal to or less than 10 wt % of a hydrogenation metal, based on thetotal weight of the carbon-carbon coupling catalyst. The zeolitecomprises 10-membered and/or 12-membered ring channels and a Silica toAlumina molar Ratio (SAR) in the range from equal to or more than 10 toequal to or less than 300.

The carbon-carbon coupling catalyst according to the invention mayherein below sometimes also be referred to as conversion catalyst. By acarbon-carbon coupling catalyst is herein preferably understood acatalyst that is capable of coupling two compounds, each of whichcompounds contains at least carbon and hydrogen, via a carbon-carbonbond under conditions suitable therefore. An example of a carbon-carboncoupling catalyst is a so-called oligomerization catalyst.

By a 10-membered respectively a 12-membered ring channel is hereinpreferably understood a channel defined by rings having 10 tetrahedralatoms respectively having 12 tetrahedral atoms in the ring. Examples oftetrahedral atoms include silicon and aluminium. The zeolite may contain10-membered ring channels, 12-membered ring channels or a combinationthereof. In addition to the 10-membered ring channels and/or 12-memberedring channels the zeolite may contain additional ring channels having adifferent number of tetrahedral atoms in the ring, preferably suchadditional ring channels are ring channels having less than 10tetrahedral atoms in the ring.

The ring channels may for example be arranged in a one-dimensional,two-dimensional or three-dimensional network.

In one embodiment the zeolite is preferably a zeolite that has a Silicato Alumina molar Ratio (SAR) in the range from equal to or more than 10to equal to or less than 100 before modification with a hydrogenationmetal, and more preferably a zeolite that has a SAR in the range fromequal to or more than 10 to equal to or less than 40 before modificationwith a hydrogenation metal. A carbon-carbon coupling catalyst with azeolite having a SAR in these ranges before modification with a metaladvantageously allows for improved stability of the catalyst towardsdeactivation. In addition the use of a carbon-carbon coupling catalystwith a zeolite having a SAR in these ranges may advantageously result ina good yield of so-called middle distillate boiling products.

In another embodiment the zeolite preferably has a Silica to Aluminamolar Ratio (SAR) in the range from equal to or more than 250 to equalto or less than 300 before modification with a hydrogenation metal. Theuse of a carbon-carbon coupling catalyst with a zeolite having a SAR inthese ranges may advantageously result in a good yield of gasolineproducts.

Preferably the zeolite is a zeolite chosen from the group consisting ofMFI-type zeolites, FER-type zeolites, BEA-type zeolites, MOR-typezeolites, FAU type zeolites and combinations thereof. By a certain typeof zeolite, such as for example an MFI-type zeolite, is hereinpreferably understood a zeolite with a certain framework type, such asfor example a zeolite with an MFI-framework type. These differentzeolite framework types are for example defined in the “Atlas of ZeoliteFramework types”, sixth revised edition, published by Elsevier B.V. in2007. Preferred examples of zeolites that can be comprised in thecarbon-carbon coupling catalyst include ZSM-5, Mordenite zeolite,zeolite Beta, Y-zeolite or combinations thereof.

The carbon-carbon coupling catalyst further comprises a hydrogenationmetal. The carbon-carbon coupling catalyst may comprise one or morehydrogenation metals. Preferably the carbon-carbon coupling catalystcomprises one or more hydrogenation metals chosen from the groupconsisting of copper, molybdenum, tungsten, cobalt and nickel. Inaddition the carbon-carbon coupling catalyst may comprise one or moreother hydrogenation metals. More preferably the carbon-carbon couplingcatalyst only contains hydrogenation metals chosen from the groupconsisting of nickel, cobalt, molybdenum, copper, tungsten andcombinations thereof.

The carbon-carbon coupling catalyst preferably comprises in the rangefrom equal to or more than 0.5 wt % to equal to or less than 10 wt %hydrogenation metal, based on the total weight of the carbon-carboncoupling catalyst. More preferably the carbon-carbon coupling catalystcomprises in the range from equal to or more than 0.5 wt % to equal toor less than 5 wt % of the hydrogenation metal, based on the totalweight of the carbon-carbon coupling catalyst. Most preferably thecarbon-carbon coupling catalyst comprises in the range from equal to ormore than 1.0 wt % to equal to or less than 3.5 wt % of thehydrogenation metal, based on the total weight of the carbon-carboncoupling catalyst.

For practical purposes the weight percentages of hydrogenation metaland/or the zeolite as specified herein are best determined based on thetotal weight of the carbon-carbon coupling catalyst before sulphiding ofthe catalyst.

In addition to the zeolite and the hydrogenation metal, thecarbon-carbon coupling catalyst may optionally comprise one or morebinders and/or fillers. An example of a binder is silica sol. Examplesof fillers include amorphous alumina, amorphous silica, or amorphoussilica-alumina, boehmite alumina (AlOOH), natural or synthetic clays,pillared or delaminated clays, or mixtures of one or more of these.Examples of clays include kaolin, hectorite, sepiolite and attapulgite.

Preferably the carbon-carbon coupling catalyst comprises equal to ormore than 70 wt %, more preferably equal to or more than 80 wt %,possibly even as high as equal to or more than 90 wt %, of the zeolite,based on the total weight of the carbon-carbon coupling catalyst. Morepreferably the carbon-carbon coupling catalyst comprises in the rangefrom equal to or more than 60.0 wt % to equal to or less than 99.9 wt %,even more preferably in the range from equal to or more than 70.0 wt %to equal to or less than 95.0 wt %, still more preferably in the rangefrom equal to or more than 70.0 wt % to equal to or less than 85.0 wt %of the zeolite, based on the total weight of the carbon-carbon couplingcatalyst. The balance may consist of one or more hydrogenation metalsand/or one or more binders and/or fillers.

The carbon-carbon coupling catalyst may be prepared in any manner knownto be suitable to the skilled person in the art to prepare a catalystcomprising a zeolite and a hydrogenation metal as described above. Forexample the carbon-carbon coupling catalyst may be prepared byion-exchange of the zeolite with an aqueous metal salt solutioncontaining the hydrogenation metal; deposition of the hydrogenationmetal on the zeolite by means of impregnation; and/or co-mulling of thezeolite and the hydrogenation metal.

In a preferred embodiment the carbon-carbon coupling catalyst isprepared by ion-exchange of the zeolite with an aqueous solutioncontaining one or more salts of one or more hydrogenation metals.Preferably the one or more hydrogenation metal(s) is/are one of thepreferred hydrogenation metals as described above. As indicated above,the most preferred hydrogenation metals include nickel, cobalt,molybdenum, copper, tungsten and combinations thereof. In addition, thecarbon-carbon coupling catalyst may contain for example ruthenium and/oriron. The aqueous solution containing one or more salts of one or morehydrogenation metals is herein also abbreviated as “metal saltsolution”. Preferably the metal salt solution is prepared by dissolvingthe one or more hydrogenation metal salts in deionized water. Preferablythe metal salt solution has a concentration in the range from equal toor more than 0.5 mol hydrogenation metal/liter water to equal to or lessthan 3 mol hydrogenation metal/liter water. Before carrying out theion-exchange, the pH of the metal salt solution is preferably adjustedto a pH in the range from equal to or more than 5 to equal to or lessthan 10, preferably by addition of an ammonium containing solution or bythe addition of aqueous ammonia.

Preferences for the zeolite are as described above. In one embodimentthe zeolite preferably has a SAR in the range from equal to or more than10 to equal to or less than 100, more preferably in the range from equalto or more than 10 to equal to or less than 40, before it is contactedwith the hydrogenation metal. Preferably the zeolite before ion exchangewith the metal salt solution, is a zeolite in the ammonium form. Azeolite in the ammonium form can for example be obtained by exchangingany known non-ammonium cations (such as H+ or Na+) by an ammonium ion orby precipitating the zeolite in the ammonium form.

Preferably the zeolite is a zeolite powder comprising crystallineparticles, which crystalline particles have a particle size distributionwith an average particle size in the range from 0.05 micrometers to 10micrometers. These crystalline particles can agglomerate into biggerparticles. The particle size can for example be determined by a laserscattering particle size distribution analyzer.

The carbon-carbon coupling catalyst may for example be prepared by aprocess comprising the steps of:

i) adding and/or suspending a zeolite, which zeolite comprises10-membered and/or 12-membered ring channels and which zeolite has aSilica to Alumina molar Ratio (SAR) in the range from equal to or morethan 10 to equal to or less than 300, into an aqueous metal saltsolution, which aqueous metal salt solution comprises in the range fromequal to or more than 0.5 to equal to or less than 3.0 mol of ahydrogenation metal per liter of water and which aqueous metal saltsolution has a pH in the range from equal to or more than 5 to equal toor less than 10, wherein the zeolite is added and/or suspended in theaqueous metal salt solution in a ratio of grams zeolite to millilitersaqueous metal salt solution in the range from equal to or more than 0.05to equal to or less than 0.33 grams of zeolite per milliliter of aqueousmetal salt solution to produce a zeolite slurry;ii) heating the zeolite slurry for a time period in the range from equalto or more than 30 minutes to equal to or less than 2 hours at atemperature in the range from equal to or more than 60° C. to equal toor less than 100° C. to produce a ion-exchanged zeolite slurry;iii) cooling the ion-exchanged zeolite slurry to a temperature equal toor below 55° C. to produce a cooled ion-exchanged zeolite slurry;iv) recovering the ion-exchanged zeolite from the cooled ion-exchangedzeolite slurry to produce a recovered ion-exchanged zeolite andoptionally washing the recovered ion-exchanged zeolite;v) drying the recovered ion-exchanged zeolite at a temperature in therange from equal to or more than 80° C. to equal to or less than 150° C.for a time period of equal to or more than 1 hour, preferably in air, toproduce a dried ion-exchanged zeolite;vi) calcining the dried ion-exchanged zeolite in air at a temperature inthe range of from equal to or more than 400° C. to equal to or less than600° C. for a time period in the range from 30 minutes to 12 hours toproduce a calcined ion-exchanged zeolite;vii) extruding the calcined ion-exchanged zeolite with a binder and/or afiller in a weight ratio of weight calcined ion-exchanged zeolite tototal weight of any binder and/or any filler in the range from equal toor more than 60:40 to equal to or less than 90:10, preferably to equalto or less than 80:20, to produce an extrudate;viii) re-calcining the extrudate at a temperature in the range fromequal to or more than 400° C. to equal to or less than 550° C. for atime period in the range from 30 minutes to 12 hours to produce acarbon-carbon coupling catalyst.

The produced carbon-carbon coupling catalyst may subsequently besulphided to produce the sulphided carbon-carbon coupling catalyst.Preferences for such sulphiding are described herein below.

In the process according to the invention, the feed is contacted withthe sulphided carbon-carbon coupling catalyst in the presence ofhydrogen at a hydrogen partial pressure of more than 1.0 MPa(MegaPascal). Preferably the feed is contacted with the sulphidedcarbon-carbon coupling catalyst in the presence of hydrogen at a partialhydrogen pressure in the range from equal to or more than 2.0 MPa toequal to or less than 20.0 MPa, more preferably between 2.5 MPa to 18.0MPa, even more preferably between 3.0 MPa and 15.0 MPa.

The hydrogen is preferably supplied as a hydrogen gas. Preferably thehydrogen is provided in the process according to the invention at ahydrogen to feed ratio in the range from equal to or more than 200 toequal to or less than 5000, more preferably in the range from equal toor more than 400 to equal to or less than 2500 Nl H₂/kg feed (normalliter hydrogen per kg feed, where a normal liter is understood to referto a liter of gas at a pressure of 0.1 MPa (MegaPascal) and at atemperature of 20° C.)

Hence, in a continuous process, instead of or in addition to contactingthe feed with the sulphided carbon-carbon coupling catalyst in thepresence of hydrogen at a hydrogen partial pressure of more than 1.0MPa, the feed may be contacted with the sulphided carbon-carbon couplingcatalyst in the presence of hydrogen at a hydrogen to feed ratio in therange from equal to or more than 200 to equal to or less than 5000 NlH₂/kg feed.

Preferably the feed is contacted with the sulphided carbon-carboncoupling catalyst at a temperature in the range from equal to or morethan 250° C. to equal to or less than 450° C., more preferably atemperature in the range from equal to or more than 280° C. to equal toor less than 380° C., even more preferably a temperature in the rangefrom equal to or more than 320° C. to equal to or less than 370° C.

Preferably the feed is contacted with the sulphided carbon-carboncoupling catalyst at a Weight Hourly Space Velocity (WHSV) in the rangefrom 0.2 to 2.5 kg feed per kg catalyst per hour.

By contacting the feed with hydrogen in the presence of the sulphidedcarbon-carbon coupling catalyst as described herein, a conversionproduct may be produced. This conversion product may herein also bereferred to as carbon-carbon coupled product. By a carbon-carbon coupledproduct is understood a product containing one or more carbon-carboncoupled compounds. An example of a carbon-carbon coupled product is anoligomerization product. The conversion product may advantageouslycontain a middle distillate boiling product. Hence, after contacting thefeed with the sulphided carbon-carbon coupling catalyst as describedherein, advantageously a middle distillate boiling product may beproduced. As indicated before, by a middle distillate boiling product isherein preferably understood a product having a boiling point at 0.1MegaPascal (MPa) in the range from equal to or more than 140° C. toequal to or less than 370° C. as determined by ASTM method D2887.Examples of such middle distillate boiling products include kerosene/jetfuel range hydrocarbons and diesel range hydrocarbons. Suitably theconversion product may contain in the range from equal to or more than30 wt %, more preferably equal to or more than 40 wt %, to equal to orless than 75 wt %, more preferably equal to or less than 65 wt %, ofmiddle distillate boiling product. The remainder may be compounds havinganother boiling point.

The conversion product may suitably contain one or more carbon-carboncoupled compounds. By a “carbon-carbon coupled compound” is hereinpreferably understood a compound that has been obtained by coupling twoother compounds via a carbon-carbon bond. Preferably the conversionproduct contains a mixture of hydrocarbon compounds. By a hydrocarboncompound is herein understood a compound containing at least carbon andhydrogen. Such a hydrocarbon compound may optionally also containheteroatoms such as oxygen, sulphur or nitrogen. In one embodiment, theaverage molecular weight of the hydrocarbon compounds in the conversionproduct is higher than the average molecular weight of the hydrocarboncompounds in the feed. Preferably the conversion product contains one ormore hydrocarbon compounds having in the range from equal to or morethan 6 carbon atoms to equal to or less than 25 carbon atoms, preferablyequal to or less than 18 carbon atoms.

The conversion product may comprise unsaturated, saturated, straightand/or branched hydrocarbon compounds. Further, the conversion productmay still contain hydrocarbon compounds comprising heteroatoms such asoxygen, sulphur and/or nitrogen. In a preferred embodiment, theconcentration of such heteroatoms in the conversion product is alreadyreduced compared to the concentration thereof in the feed. In anespecially preferred embodiment the conversion product contains alreadyless than 100 ppmw or essentially no oxygen.

It may be considered advantageous to increase the saturation and/or thebranching of the one or more hydrocarbon compounds in the conversionproduct and/or to reduce the content of oxygen, sulphur and/or nitrogentherein. And even when the conversion product contains less than 100ppmw or essentially no oxygen, it may be still be consideredadvantageous to increase the saturation and/or the branching of thehydrocarbon compounds in the carbon-carbon coupled product.

In a preferred embodiment the process according to the inventiontherefore further comprises contacting the conversion product withhydrogen in the presence of a hydrotreating and/or hydroisomerizationcatalyst.

By a hydrotreating catalyst is preferably understood a catalyst that iscapable of converting unsaturated carbon-carbon bonds into saturatedcarbon-carbon bonds and/or a catalyst that is capable of removingheteroatoms such as oxygen, nitrogen and sulphur. Preferably thehydrotreating catalyst is a hydrodeoxygenation catalyst, ahydrodesulphurization catalyst and/or a hydrodenitrogenation catalyst.

By a hydroisomerization catalyst is preferably understood a catalystthat is capable of converting unbranched hydrocarbon compounds intobranched hydrocarbon compounds and/or of converting mono-branchedhydrocarbon compounds into multiple branched hydrocarbon compounds.

The hydrotreating and/or hydroisomerization catalyst can be anyhydrotreating and/or hydroisomerization catalyst known to be suitablefor the purpose of hydrotreating and/or hydroisomerization by the personskilled in the art. Preferably the hydrotreating catalyst and/orhydroisomerization catalyst are sulphided. Such sulfurization can becarried out as described herein below.

In one preferred embodiment the hydrotreating and/or hydroisomerizationcatalyst comprises, nickel or cobalt promoted, molybdenum or tungsten ona support. Examples of such catalysts include sulphidednickel-molybdenum on a support; sulphided cobalt-molybdenum on asupport; sulphided nickel-tungsten on a support; and sulphidedcobalt-tungsten on a support. The support preferably comprises a metaloxide, such as alumina, silica or silica alumina. Preferably the supportcontains in the range from equal to or more than 0 wt % to equal to orless than 30 wt % of a zeolite; and/or in the range from equal to ormore than 0 wt % to equal to or less than 50 wt % of amorphous silica,alumina or silica alumina. The remainder may be another filler and/or abinder. If the hydroisomerization and/or hydrotreating catalyst containsalumina, this alumina is preferably gamma-alumina.

In another preferred embodiment the hydrotreating and/orhydroisomerization catalyst may comprise phosphor. For example thehydrotreating and/or hydroisomerization catalyst may comprise nickelphosphide supported on alumina or carbon.

As a result of the hydrotreatment/hydroisomerization the percentage ofsaturated and/or branched hydrocarbon compounds in the conversionproduct may be increased; and/or the content of non-carbon, non-hydrogenatoms such as sulphur, nitrogen and/or oxygen in the conversion productmay be reduced.

Any hydrotreatment and/or hydroisomerization is preferably carried outat a temperature in the range from 250° C. to 380° C.; a hydrogenpartial pressure in the range from 1 to 15 MPa (MegaPascal); a WeightHourly Space Velocity (WHSV) in the range from 0.2 kg liquid feed/(kgcatalyst·hr) to 2.5 kg liquid feed/(kg catalyst·hr); and/or a hydrogento liquid feed ratio in the range from 200 Nl hydrogen/kg liquid feed to3000 Nl hydrogen/kg liquid feed (in this step the feed may be the liquidconversion product).

Preferably the weight ratio of sulphided carbon-carbon coupling catalystto (preferably sulphided) hydrotreating catalyst and/or (preferablysulphided) hydroisomerization catalyst lies in the range from equal toor more than 1:1 to equal to or less than 4:1.

After hydrotreatment and/or hydroisomerization a hydrotreated and/orhydroisomerized conversion product may be obtained. Such hydrotreatedand/or hydroisomerized conversion product may have an increasedpercentage of saturated and/or branched hydrocarbon compounds and/or areduced content of non-carbon, non-hydrogen atoms such as sulphur,nitrogen and/or oxygen.

In a preferred embodiment the hydrotreated and/or hydroisomerizedconversion product is a mixture containing one or more n-paraffinic,isoparaffinic, olefinic, naphthenic, and/or aromatic hydrocarboncompounds.

The content of olefinic hydrocarbon compounds in the hydrotreated and/orhydroisomerized conversion product preferably varies from equal to ormore than 0 wt % to equal to or less than 10 wt %, based on the totalweight of the hydrotreated and/or hydroisomerized conversion product.

The content of aromatic hydrocarbon compounds in the hydrotreated and/orhydroisomerized conversion product preferably varies from equal to ormore than 0.1 wt % to equal to or less than 45 wt %, based on the totalweight of the hydrotreated and/or hydroisomerized conversion product.

The content of naphthenic hydrocarbon compounds in the hydrotreatedand/or hydroisomerized conversion product preferably varies from equalto or more than 0.1 wt % to equal to or less than 45 wt %, based on thetotal weight of the hydrotreated and/or hydroisomerized conversionproduct.

The content of n-paraffinic hydrocarbon compounds in the hydrotreatedand/or hydroisomerized conversion product preferably varies from equalto or more than 0.5 wt % to equal to or less than 75 wt %, based on thetotal weight of the hydrotreated and/or hydroisomerized conversionproduct.

The content of isoparaffinic hydrocarbon compounds in the hydrotreatedand/or hydroisomerized conversion product preferably varies from equalto or more than 0.5 wt % to equal to or less than 50 wt % (wt % refersto percentage by weight), based on the total weight of the hydrotreatedand/or hydroisomerized conversion product.

In addition to carbon and hydrogen, the hydrotreated and/orhydroisomerized conversion product may contain other atoms such assulfur, nitrogen and oxygen. However, the sulfur content of thehydrotreated and/or hydroisomerized conversion product is preferablyreduced to a content of less than 100 ppmw, more preferably less than 10ppmw. The nitrogen content of the hydrotreated and/or hydroisomerizedconversion product is preferably reduced to a content less than 300ppmw, and more preferably to less than 50 ppmw. The oxygen content ofthe hydrotreated and/or hydroisomerized conversion product is preferablyreduced to a content of less than 2 wt %, preferably less than 0.5 wt %,and most preferably less than 0.2 wt %.

A middle distillate boiling product can conveniently be obtained froman, optionally hydrotreated and/or hydroisomerized, conversion productby any means known to be suitable by the person skilled in the art. Suchmeans include for example fractionation, distillation and/or phaseseparation.

The process according to the invention may advantageously be used toprepare a plurality of hydrocarbon compounds that may be of use as abiofuel component and/or a biochemical component.

In a preferred embodiment therefore at least part of the, conversionproduct (obtained after contacting the feed with the sulphidedcarbon-carbon coupling catalyst) and/or at least part of thehydrotreated and/or hydroisomerized conversion product (obtained afterfurther hydrotreatment and/or further hydroisomerization of suchconversion product) is blended with one or more other components andused in a fuel. For example a, preferably hydrotreated and/orhydroisomerized, middle distillate boiling product may be blended withone or more additives to produce a biofuel.

The carbon-carbon coupling catalyst and optionally any hydrogenationcatalyst and/or any hydrotreating catalyst and/or hydroisomerizationcatalyst may suitably be sulphided ex-situ (i.e. outside the process) orin-situ (i.e. during the process) or both to produce a sulphidedcarbon-carbon coupling catalyst, respectively a sulphidedhydrogenation-, sulphided hydrotreating- and/or a sulphidedhydroisomerization-catalyst.

In one preferred embodiment the respective catalyst(s) is/are sulphidedby a liquid phase sulphiding procedure. In such a liquid phasesulphiding procedure the respective catalyst(s) is/are contacted with aliquid containing in the range from equal to or more 0.1 wt % to equalto or less than 3.5 wt % of sulphur, more preferably in the range fromequal to or more than 1.5 wt % to equal to or less than 3.5 wt % ofsulphur at a temperature in the range from equal to or more than 200° C.to equal to or less than 400° C., more preferably at a temperature inthe range from equal to or more than 300° C. to equal to or less than380° C., in the presence of hydrogen.

The sulphur-containing liquid can for example be the feed containing theone or more C3-C12 oxygenates, which may be spiked with sulphur, or forexample another hydrocarbon containing liquid that additionally containssulphur.

A preferred example of such a hydrocarbon containing liquid thatadditionally contains sulphur is a so-called straight run gasoilcontaining sulphur. Conveniently the liquid phase sulphiding with such ahydrocarbon containing liquid that additionally contains sulphur may becarried out in a reactor, where a catalyst is first sulphided in thereactor by contacting it with the hydrocarbon-containing liquid andsubsequently the hydrocarbon-containing liquid is replaced by the feedcomprising the one or more C3-C12 oxygenates.

In another preferred embodiment the respective catalyst(s) is/aresulphided by spiking the feed comprising the one or more C3-C12oxygenates with sulphur containing compounds to produce a feedcontaining in the range from equal to or more than 0.1 wt % to equal toor less than 0.2 wt % sulphur and preferably maintaining this sulphurlevel throughout the process. Examples of such one or more sulphurcontaining compounds include dimethyldisulphide (DMDS) or SULFRZOL® 54(SULFRZOL® 54 is a trademark, the sulphur containing compound iscommercially available from Lubrizol).

In a further preferred embodiment sulphiding of the respectivecatalyst(s) can be accomplished by gas-phase sulphiding with a H₂S/H₂mixture as the sulfiding medium. Such a H₂S/H₂ mixture preferablycomprises in the range from 0.1 and 5 vol % H₂S based on the totalvolume of the H₂S/H₂ mixture.

One skilled in the art will understand that a combination of the abovepreferred sulphiding embodiments is also possible.

In a preferred embodiment the sulphided catalyst(s) is/are kept in thesulphided state by carrying out the process in the presence ofhydrogensulphide. The hydrogensulphide may be provided as such or may begenerated in-situ by hydrogenation of the feed or a co-feed. In apreferred embodiment the hydrogensulphide may be generated by spikingthe feed with one or more sulphur containing compounds. Preferably thefeed may be spiked with an amount of sulphur in the range form equal toor more than 0.1 wt % to equal to or less than 0.2 wt %. Examples ofsuch one or more sulphur containing compounds include dimethyldisulphide(DMDS) or SULFRZOL® 54 (SULFRZOL® 54 is a trademark, the sulphurcontaining compound is commercially available from Lubrizol).

The process according to the invention may for example be carried out asa batch process, a semi-batch process or a continuous process.Preferably the process according to the invention is a continuousprocess.

The process according to the invention may be carried out in any kind ofreactor, including for example a fixed bed reactor or a moving,ebullated or slurry bed reactor.

In a preferred embodiment the process according to the invention iscarried out in a fixed bed reactor. The fixed bed reactor may forexample comprise a stacked bed configuration containing a catalyst bedwith the carbon-carbon coupling catalyst in combination with one or moreother catalyst beds containing other catalysts. For example the reactormay comprise a catalyst bed containing the carbon-carbon couplingcatalyst, optionally preceded by a catalyst bed containing ahydrogenation catalyst and/or optionally followed by one or morecatalyst beds containing a hydrotreatment and/or hydroisomerizationcatalyst. In a preferred embodiment the sulphided carbon-carbon couplingcatalyst and a (preferably sulphided) hydrotreating catalyst and/or a(preferably sulphided) hydroisomerization catalyst are combined in astacked bed configuration, where the sulphided carbon-carbon couplingcatalyst is located upstream of the (preferably sulphided) hydrotreatingcatalyst and/or (preferably sulphided) hydroisomerization catalyst.

In a preferred embodiment the invention further provides a processcomprising:

1) a carbon-carbon coupling step, wherein a feed comprising one or moreC3-C12 oxygenates is contacted with hydrogen at a hydrogen partialpressure of at least 0.1 MegaPascal (MPa), preferably at a hydrogenpartial pressure of at least 1.0 MPa, in the presence of a sulphidedcarbon-carbon coupling catalyst as described herein to produce aconversion product;2) a hydrotreatment and/or hydroisomerization step, wherein at leastpart of the conversion product is contacted with hydrogen in thepresence of a sulphided hydrotreating catalyst and/or a sulphidedhydroisomerization catalyst to produce a hydrotreated and/orhydroisomerized conversion product; and3) an optional purification step, wherein the hydrotreated and/orhydroisomerized conversion product is purified to obtain a finalproduct.

As indicated above, such a process may be preceded by a partialhydrogenation step comprising contacting a feed containing one or moreC3-C12 oxygenates with a source of hydrogen in the presence of asulphided hydrogenation catalyst to produce a partially hydrogenatedeffluent comprising one or more partially hydrogenated C3-C12oxygenates, whereafter this partially hydrogenated effluent is forwardedas a feed comprising one or more C3-C12 oxygenates to the abovecarbon-carbon coupling step (step 1).

Conveniently each of the above steps may be carried out in a separatecatalyst bed. These catalyst beds may be combined in one or morereactors or may be located in separate reactors.

Preferences are as described further herein. The hydrogen is preferablysupplied as a hydrogen gas. Advantageously the hydrogen may compriserecycled hydrogen obtained from steam reforming C1-C3 hydrocarboncompounds that may be co-produced in the process of the invention.

The process according to the invention further provides a processwherein the, optionally hydrotreated and/or hydroisomerized, conversionproduct is phase separated to produce a gasphase comprising C1-C3hydrocarbon compounds, an aqueous phase, and a liquid hydrocarbon phase,which liquid hydrocarbon phase may comprise one or more C4+-hydrocarboncompounds (i.e. hydrocarbon compounds comprising 4 or more carbonatoms).

The gasphase may comprise unreacted hydrogen. This unreacted hydrogenmay advantageously be separated from the gasphase and recycled as asource of hydrogen to the process.

As indicated, in a preferred embodiment the C1-C3 hydrocarbon compoundsfrom the gasphase can be forwarded to a steam reformer (also sometimesreferred to as steam methane reformer) to produce hydrogen. Hence, in apreferred embodiment the process according to the invention furtherproduces a C1-C3 hydrocarbon product, which C1-C3 hydrocarbon product isconverted in a steam reformer to produce hydrogen. Preferably theproduced hydrogen is recycled to the process.

Depending on its composition, the liquid hydrocarbon phase may becontacted with a further source of hydrogen in an additional catalystbed containing one or more additional hydrotreating catalyst(s).

One example of a process according to the invention has been illustratedin FIG. 1. In FIG. 1 a feed comprising one or more C3-C12 ketones (102)and a hydrogen gas (104) are supplied to a reactor (110) comprising astacked bed comprising a first catalyst bed (111 a) containing asulphided hydrogenation catalyst (111 b); a second catalyst bed (112 a)containing a sulphided carbon-carbon coupling catalyst (112 b), a thirdcatalyst bed (113 a) containing a sulphided hydrotreating catalyst (113b) and a fourth catalyst bed (114 a) containing a sulphidedhydroisomerization catalyst (114 b). In the reactor (110) the feed (102)is contacted with the hydrogen gas (104). In the first catalyst bed (111a) containing the sulphided hydrogenation catalyst (111 b) the one ormore C3-C12 ketones from the feed (102) are hydrogenated in order toconvert them into one or more C3-C12 alkanols, without completehydrodeoxygenation. In addition sulphur and or nitrogen may be removedfrom the feed. In the second catalyst bed (112 a) containing a sulphidedcarbon-carbon coupling catalyst (112 b) the C3-C12 alkanols and anyunconverted C3-C12 ketones are carbon-carbon coupled into compoundshaving a higher molecular weight than the C3-C12 ketones in the feed.For example the ketones and/or alkanols may undergo reactions such asoligomerization or concatenation reactions, aldol condensationreactions, cyclization reactions and/or aromatization reactions. In thethird catalyst bed (113 a) containing the sulphided hydrotreatingcatalyst (113 b) the effluent of the previous catalyst beds is furtherhydrodeoxygenated. Since the product of the first two catalyst beds (111a and 112 a) is a mixture of compounds consisting only of carbon andhydrogen and compounds containing hydrogen, carbon and oxygen, and sinceit is desired that the final product be a product comprising onlycompounds consisting of carbon and hydrogen, oxygen and otherheteroatoms are removed in the third catalyst bed (113 a) with the helpof the sulphided hydrotreating catalyst (113 b). In the third catalystbed (113 a) also hydrogenation of unsaturates such as olefins andaromatics is accomplished and a saturated hydrocarbon product containingessentially no heteroatoms is obtained. Finally, especially with a feedcontaining 2-ketones, the product of the third catalyst bed (113 a) maycontain hydrocarbon compounds that are linear or have only methylbranching on the second carbon atom. Such unbranched or minimallybranched hydrocarbon compounds may have poor octane numbers and highpour points. In the fourth catalyst bed (114 a) containing the sulphidedhydroisomerization catalyst (114 b) these linear or minimally branchedhydrocarbon compounds are therefore hydroisomerized to increase octanenumber and decrease pour point.

Contacting of the feed (102) and the hydrogen gas (104) in the reactor(110) is carried out under a hydrogen atmosphere at a hydrogen partialpressure in the range from 8.0 to 15.0 MegaPascal and a temperature inthe range from 320° C. to 400° C. As explained herein, the elevatedhydrogen partial pressure helps in retarding the deactivation of thesulphided carbon-carbon coupling catalyst due to coke formation.

The effluent (116) from the reactor (110) is separated in separator(118) into a hydrocarbon liquid phase (120), an aqueous phase (122), anda gasphase (124). The gasphase (124) contains hydrogen, saturated C1-C3hydrocarbon compounds, hydrogen sulphide (H2S), ammonia (NH3),carbonmonoxide (CO), carbon dioxide (CO2) and carbonylsulphide (COS).The gasphase (124) is forwarded to a purification and steam reformersection (126). The saturated C1-C3 hydrocarbon compounds are used as afeed for the steam reformer in section (126). In the steam reformer ofsection (126) hydrogen gas is generated that can be convenientlyrecycled to the reactor (110) as a source of hydrogen (104).

In FIG. 2 another example of the process according to the invention hasbeen illustrated.

In FIG. 2 a feed (202) comprising one or more C3-C12 ketones and ahydrogen gas (204) are supplied to a reactor (210) comprising a stackedbed comprising a first catalyst bed (211 a) containing a sulphidedcarbon-carbon coupling catalyst (211 b) and a second catalyst bed (212a) containing a sulphided hydrotreating catalyst (212 b). In the reactor(210) the feed (202) is contacted with the hydrogen gas (204). In thefirst catalyst bed (211 a) containing the sulphided carbon-carboncoupling catalyst (211 b) the one or more C3-C12 ketones from the feed(202) are carbon-carbon coupled into compounds having a higher molecularweight than the C3-C12 ketones in the feed. For example the ketones mayundergo reactions such as for example oligomerization reactions,cyclization reactions and/or aromatization reactions. In the secondcatalyst bed (212 a) containing the sulphided hydrotreating catalyst(212 b) any unsaturated compounds in the effluent of the previouscatalyst bed are saturated and any residual heteroatoms such as oxygen,sulfur and/or nitrogen are removed. Reaction conditions are similar asfor the process in FIG. 1.

Similar as for the process in FIG. 1, the effluent (216) from thereactor (210) is separated in separator (218) into a hydrocarbon liquidphase (220), an aqueous phase (222), and a gasphase (224). The gasphase(224) contains hydrogen, saturated C1-C3 hydrocarbon compounds, hydrogensulphide (H2S), ammonia (NH3), carbonmonoxide (CO), carbon dioxide (CO2)and carbonylsulphide (COS). The gasphase (224) is forwarded to apurification and steam reformer section (226). The saturated C1-C3hydrocarbon compounds are used as a feed for the steam reformer in(226). In the steam reformer in (226) hydrogen gas is generated that canbe conveniently recycled to the reactor (210) as a source of hydrogen(204).

In FIG. 3 another example of a process according to the invention hasbeen provided. In FIG. 3 a feed (302) comprising one or more C3-C12ketones and a gas stream (304) containing hydrogen and C1-C3 gases(possibly including any unsaturated C2-C3 gases) are supplied to a firstreactor (310) comprising a stacked bed comprising a first catalyst bed(311 a) containing a sulphided hydrogenation catalyst (311 b) and asecond catalyst bed (312 a) containing a sulphided carbon-carboncoupling catalyst (312 b). In the reactor (310) the feed (302) iscontacted with the hydrogen gas from gas stream (304). In the firstcatalyst bed (311 a) containing the sulphided hydrogenation catalyst(311 b) the one or more C3-C12 ketones from the feed (302) are partiallyor wholly hydrogenated into C3-C12 alkanols without carrying out acomplete hydrodeoxygenation. The sulphided hydrogenation catalyst (311b) may also remove heteroatoms such as sulphur and nitrogen from thefeed (302). In the second catalyst bed (312 a) containing a sulphidedcarbon-carbon coupling catalyst (312 b) the C3-C12 alkanols and anyunconverted C3-C12 ketones are carbon-carbon coupled into compoundshaving a higher molecular weight than the C3-C12 ketones in the feed.For example in the second catalyst bed (312 a) reactions such as thedehydration of alcohols to produce olefins and the oligomerization ofolefins to produce larger hydrocarbons are carried out. In additionunconverted ketones can be converted into hydrocarbons or oxygenateswith a higher molecular weight. The product of the second catalyst bed(312 a) and the product of the first reactor (310) may thereforecomprise hydrocarbon compounds consisting only of carbon and hydrogen,but also oxygenated compounds (that is, compounds containing hydrogen,carbon and oxygen). The effluent (316) from the reactor (310) isseparated in separator (318) into a hydrocarbon liquid phase (320), anaqueous phase (322), and a gasphase (324).

Part of the gasphase (324) may be purged via purge stream (328) andanother part of the gasphase may be recycled via recycle compressor(330) to gas stream (304). Fresh hydrogen can be added via hydrogenmake-up stream (332).

The hydrocarbon liquid phase (320) is forwarded to a second reactor(340). The second reactor (340) contains a catalyst bed (342 a)containing a sulphided hydrotreatment catalyst (342 b). In the secondreactor (340) a gas stream containing fresh or recycled hydrogen (344)is contacted with the hydrocarbon liquid phase (320) in the presence ofthe hydrotreatment catalyst (342 b) to remove any residual oxygen fromthe hydrocarbon liquid phase (320) and to saturate any olefins andaromatics. In addition to a sulphided hydrotreatment catalyst (342 b) ina top catalyst bed, the second reactor (340) may optionally contain asulphided hydroisomerization catalyst in a bottom catalyst bed (notshown) to hydroisomerize n-paraffins and/or n-olefins obtained from thesulphided hydrotreatment catalyst in the top bed. It is also possible toomit the first sulphided hydrogenation catalyst (311 b) in the firstreactor (310) and contact the ketones directly with the sulphidedcarbon-carbon coupling catalyst (312 b).

The effluent (346) from the second reactor can be separated in a secondseparator (348) into a gasphase (350) and a hydrocarbon liquid product(352).

An advantage of the two reactor line-up of FIG. 3 is the ability torecycle unsaturated C2-C3 gases which can be oligomerized. Since in thetwo-reactor line-up of FIG. 3 the hydrotreatment catalyst is situated ina separate second reactor, the hydrocarbons coming from the firstreactor may remain unsaturated. After recycling, C2-C3 hydrocarboncompounds that are unsaturated can oligomerize further into gasoline anddiesel range hydrocarbons. Recycling of the unsaturated C2-C3hydrocarbon compounds thus helps in increasing overall liquid fuelyields.

In FIG. 4 another example of a process according to the invention hasbeen provided. In FIG. 4 a feed (402) comprising one or more C3-C12ketones and a gas stream (404) containing hydrogen and C1-C3 gases(possibly including any unsaturated C2-C3 gases) are supplied to a firstreactor (410) comprising a first catalyst bed (411 a) containing asulphided carbon-carbon coupling catalyst (411 b). In the reactor (410)the feed (402) is contacted with the hydrogen gas from gas stream (404)in the presence of the sulphided carbon-carbon coupling catalyst (411b). In the first catalyst bed (411 a) containing the sulphidedcarbon-carbon coupling catalyst (411 b) the one or more C3-C12 ketonesfrom the feed (402) are carbon-carbon coupled into compounds having ahigher molecular weight than the C3-C12 ketones in the feed.

The product of the first catalyst bed (411 a) and the product of thefirst reactor (410) may therefore comprise hydrocarbon compoundsconsisting only of carbon and hydrogen, but also oxygenated compounds(that is, compounds containing hydrogen, carbon and oxygen). Theeffluent (416) from the reactor (410) is separated in separator (418)into a hydrocarbon liquid phase (420), an aqueous phase (422), and agasphase (424).

Part of the gasphase (424) may be purged via purge stream (428) andanother part of the gasphase may be recycled via recycle compressor(430) to gas stream (404). Fresh hydrogen can be added via hydrogenmake-up stream (432).

The hydrocarbon liquid phase (420) is forwarded to a distillation column(434), where it is separated into a light fraction (436) containinghydrocarbon compounds having equal to or less than 5 carbon atoms and aheavy fraction (438) containing hydrocarbon compounds having equal to ormore than 6 carbon atoms. Part of the light fraction (436) may be purgedvia purge stream (437) and another part of the light fraction (436) maybe recycled to the first reactor (410).

The heavy fraction (438) can be forwarded to second reactor (440). Thesecond reactor (440) contains a second catalyst bed (442 a) containing asulphided hydrotreatment catalyst (442 b). In the second reactor (440) agas stream containing fresh or recycled hydrogen (444) is contacted withthe heavy fraction (438) in the presence of the sulphided hydrotreatmentcatalyst (442 b) to remove any residual oxygen from the heavy fraction(438) and to saturate any olefins and aromatics. In addition to asulphided hydrotreatment catalyst (442 b) in a top catalyst bed, thesecond reactor (440) may optionally contain a sulphidedhydroisomerization catalyst in a bottom catalyst bed (not shown) tohydroisomerize n-paraffins and/or n-olefins obtained from thehydrotreatment catalyst in the top bed. The effluent (446) from thesecond reactor (440) can be separated in a second separator (448) into agasphase (450), a hydrocarbon liquid product (452) containing jetfuelrange hydrocarbons and an aqueous phase (454). The gasphase (450) mayoptionally be sent to recycle compressor (430) (not shown).

EXAMPLES Examples 1a and 1b: Conversion of a Mixed Ketone Feed in aStacked Bed Containing a Nickel-Exchanged Mordenite Zeolite Catalyst(Carbon-Carbon Coupling Catalyst A) and a Hydrotreatment Catalyst

A powder of mordenite zeolite with an ammonium form and an SiO2:Al2O3molar ratio (SAR) of approximately 20 was obtained commercially fromZeolyst International. An aqueous solution of 1 mol/liter nickel (II)nitrate hexahydrate was prepared and the pH of the solution was adjustedto 6 using ammonium hydroxide. The powder of mordenite zeolite wassuspended in nickel nitrate solution in an amount of about 10 ml ofnickel nitrate solution to about 1 gram of mordenite powder and theslurry was vigorously agitated using a stirrer or impeller to get auniform suspension. Subsequently the temperature of the slurry wasraised to 95° C. while refluxing and then maintained at 95° C. for 1hour. The slurry was vigorously agitated using a stirrer or impellerduring the whole of the ion-exchange step. Hereafter the slurry wascooled to 50° C., filtered to recover nickel-exchanged mordenite powderand washed with water.

The recovered nickel-exchanged mordenite powder was calcined at atemperature of 500° C. for 2 hours. Extrudates were prepared by mixingCATAPAL-D boehmite alumina (CATAPAL is a trademark, CATAPAL-D boehmitealumina is commercially obtainable from Sasol) in a ratio of 80 wt %nickel-exchanged Mordenite to 20 wt % alumina (80:20). The obtainedextrudates were re-calcined at 500° C. during 2 hours. The preparednickel-exchanged mordenite zeolite catalyst contained about 1.5 wt %nickel on the basis of the total weight of the catalyst (carbon-carboncoupling catalyst A).

The prepared 1.5 wt % nickel-exchanged mordenite zeolite catalyst(carbon-carbon coupling catalyst A) was loaded into a stacked bedconfiguration in a reactor.

The stacked bed configuration consisted of a top catalyst bed consistingof the carbon-carbon coupling catalyst A and a bottom catalyst bedcomprising a nickel-molybdenum hydrotreating catalyst containing about18 wt % molybdenum, about 6 wt % nickel and about 3 wt % phosphor onalumina (herein also referred to as 6Ni-18Mo/Al) in a weight ratio ofcarbon-carbon coupling catalyst A to nickel-molybdenum hydrotreatingcatalyst of about 1.95:1. In this configuration the top catalyst bed waslocated upstream of the bottom catalyst bed.

After the catalysts were loaded in the reactor, they were sulphided witha gasoil spiked with dimethyldisulphide (DMDS) to have a sulphur contentof 2.5 wt % using a liquid phase sulphiding procedure by exposing thecatalyst to the sulphur-containing gasoil and hydrogen at a temperatureof about 345° C. for a period of about 12 hours at a pressure of 12 MPa.

After sulphiding of the catalysts, a feed containing a mixture ofketones having predominantly 3 to 11 carbon atoms as illustrated intable 1 (hereafter also referred to as “mixed ketone feed”) wascontacted with the catalysts at the conditions summarized in table 2 forexamples 1a and 1b. The feed containing the mixture of ketones wasderived from the fermentation of food waste (a mixture of animal andplant derived lignocellulosic biomass, proteins, fats and oils etc.).The mixed ketone feed had a total sulphur content of about 391 ppmw anda total nitrogen content of about 3350 ppmw, out of which the basicnitrogen content was about 914 ppmw. The mixed ketone feed was spikedwith DMDS to increase its sulfur content to about 0.1% wt.

After contacting the mixed ketone feed with the catalysts, reactoreffluent was collected.

A liquid hydrocarbon product was separated from the reactor effluent.Product characteristics for the liquid hydrocarbon product obtained arelisted in table 3 for examples 1a and 1b.

In the below tables, the abbreviation “CCC cat.” refers to the“carbon-carbon coupling catalyst”; and the abbreviation “HT cat.” refersto the “hydrotreatment catalyst”.

TABLE 1 Mixed Ketone Feed Composition Component Wt % Acetone 14.642-butanone 18.19 3-butanone, 3- 0.90 methyl 2-pentanone 22.53 Methylisobutyl 2.76 ketone 3-hexanone 4.70 2-hexanone 6.81 4-heptanone 1.803-heptanone 1.42 2-heptanone 4.18 4-octanone 1.02 3-octanone 0.842-octanone 0.93 4-nonanone 0.64 3-Nonanone 0.22 2-Nonanone 0.184-decanone 0.18 3-decanone 0.03 2-decanone 0.07 6-undecanone 0.08

Examples 2a and 2b: Conversion of a Mixed Ketone Feed in a Stacked BedContaining a Cobalt-Exchanged Mordenite Zeolite Catalyst (Carbon-CarbonCoupling Catalyst B) and a Hydrotreatment Catalyst

A powder of mordenite zeolite with an ammonium form and an SiO2:Al2O3molar ratio (SAR) of approximately 20 was obtained commercially fromZeolyst International. An aqueous solution of 1 mol/liter cobalt (II)nitrate hexahydrate was prepared and the pH of the solution was adjustedto 6 using ammonium hydroxide. The powder of mordenite zeolite wassuspended in cobalt nitrate solution in an amount of about 10 ml ofcobalt nitrate solution to about 1 gram of mordenite powder and theslurry was vigorously agitated using a stirrer or impeller to get auniform suspension. Subsequently the temperature of the slurry wasraised to 95° C. while refluxing and then maintained at 95° C. for 1hour. The slurry was vigorously agitated using a stirrer or impellerduring the whole of the ion-exchange step. Hereafter the slurry wascooled to 50° C., filtered to recover cobalt-exchanged mordenite powderand washed with water.

The recovered cobalt-exchanged mordenite powder was calcined at atemperature of 500° C. for 2 hours. Extrudates were prepared by mixingCATAPAL-D boehmite alumina (CATAPAL is a trademark, CATAPAL-D boehmitealumina is commercially obtainable from Sasol) in a ratio of 80 wt %cobalt-exchanged mordenite to 20 wt % alumina (80:20). The obtainedextrudates were re-calcined at 500° C. during 2 hours. The preparedcobalt-exchanged mordenite zeolite catalyst contained about 2 wt %cobalt on the basis of the total weight of the catalyst (carbon-carboncoupling catalyst B).

The prepared 2 wt % cobalt-exchanged mordenite zeolite catalyst(carbon-carbon coupling catalyst B) was loaded into a stacked bedconfiguration in a reactor as illustrated in FIG. 2, with the exceptionthat no gas was recycled. The stacked bed configuration consisted of atop catalyst bed consisting of the carbon-carbon coupling catalyst B anda bottom catalyst bed comprising the same nickel-molybdenumhydrotreating catalyst as used in examples 1a and 1b in a weight ratioof carbon-carbon coupling catalyst B to nickel-molybdenum hydrotreatingcatalyst of 1.87:1. The top catalyst bed was located upstream of thebottom catalyst bed.

After the catalysts were loaded in the reactor, they were sulphided witha gasoil spiked to have a sulphur content of 2.5 wt % using a liquidphase sulphiding procedure by exposing the catalyst to thesulphur-containing gasoil and hydrogen at a temperature of about 345° C.for a period of about 12 hours at a pressure of 12 MPa.Dimethyldisulphide (DMDS) was used to spike the gasoil with sulfur toobtain a sulfur content of 2.5 wt %.

After sulphiding of the catalysts, a feed identical to that in examples1a and 1b, containing a mixture of ketones having predominantly 3 to 11carbon atoms as illustrated in table 1, was contacted with the catalystsat the conditions summarized in table 2 for examples 2a and 2b.

After contacting the mixed ketone feed with the catalysts, reactoreffluent was collected.

A liquid hydrocarbon product was separated from the reactor effluent.Product characteristics for the liquid hydrocarbon product obtained arelisted in table 3 for examples 2a and 2b.

The boiling point distribution of the liquid hydrocarbon productobtained in example 2b (using a reaction temperature of 350° C.) wasanalyzed according to ASTM method D2887. The result is illustrated inFIG. 5. As can be seen in FIG. 5, the obtained boiling curve is smoothin the boiling range from 130° C. to 370° C. A smooth boiling pointdistribution, or lack of distinctive steps in such a boiling pointdistribution, is advantageous to achieve a suitable productspecification (such as Jet A1 or JP8) for use in jet fuel.

Examples 3a and 3b: Conversion of a Mixed Ketone Feed in a Stacked BedContaining a Nickel-Exchanged Zeolite Beta Catalyst (Carbon-CarbonCoupling Catalyst C) and a Hydrotreatment Catalyst

A powder of zeolite Beta with an ammonium form and an SiO2:Al2O3 molarratio (SAR) of approximately 20 was obtained commercially from ZeolystInternational. An aqueous solution of 1 mol/liter nickel (II) nitratehexahydrate was prepared and the pH of the solution was adjusted to 6using ammonium hydroxide. The zeolite Beta powder was suspended in thenickel nitrate solution in an amount of about 10 ml of nickel nitratesolution to about 1 gram of zeolite Beta powder and the slurry wasvigorously agitated using a stirrer or impeller to get a uniformsuspension. Subsequently the temperature of the slurry was raised to 95°C. while refluxing and then maintained at 95° C. for 1 hour. The slurrywas vigorously agitated using a stirrer or impeller during the whole ofthe ion-exchange step. Hereafter the slurry was cooled to 50° C.,filtered to recover nickel-exchanged zeolite Beta powder and washed withwater.

The recovered nickel-exchanged zeolite Beta powder was calcined at atemperature of 500° C. for 2 hours. Extrudates were prepared by mixingCATAPAL-D boehmite alumina (CATAPAL is a trademark, CATAPAL-D boehmitealumina is commercially obtainable from Sasol) in a ratio of 80 wt %nickel-exchanged zeolite Beta to 20 weight % alumina (80:20). Theobtained extrudates were re-calcined at 500° C. during 2 hours. Theprepared nickel-exchanged zeolite Beta catalyst contained about 1.8 wt %nickel on the basis of the total weight of the catalyst (carbon-carboncoupling catalyst C).

The prepared 1.8 wt % nickel-exchanged zeolite Beta catalyst(carbon-carbon coupling catalyst C) was loaded into a stacked bedconfiguration in a reactor as illustrated in FIG. 2, with the exceptionthat no gas was recycled. The stacked bed configuration consisted of atop catalyst bed consisting of the carbon-carbon coupling catalyst C anda bottom catalyst bed comprising the same nickel-molybdenumhydrotreating catalyst as used in examples 1a and 1b in a weight ratioof carbon-carbon coupling catalyst C to nickel-molybdenum hydrotreatingcatalyst of 1.59:1. The top catalyst bed was located upstream of thebottom catalyst bed.

After the catalysts were loaded in the reactor, they were sulphided witha gasoil spiked with dimethyldisulphide (DMDS) to have a sulphur contentof 2.5 wt % using a liquid phase sulphiding procedure by exposing thecatalyst to the sulphur-containing gasoil and hydrogen at a temperatureof about 345° C. for a period of about 12 hours at a pressure of 12 MPa.

After sulphiding of the catalysts, a feed identical to that in examples1a and 1b, containing a mixture of ketones having predominantly 3 to 11carbon atoms as illustrated in table 1 was contacted with the catalystsat the conditions summarized in table 2 for examples 3a and 3b.

A liquid hydrocarbon product was separated from the reactor effluent.Product characteristics for the liquid hydrocarbon product obtained arelisted in table 3 for examples 3a and 3b.

The boiling point distribution of the liquid hydrocarbon productobtained in example 3b (i.e. using a reaction temperature of 350° C.)was analyzed according to ASTM method D2887. The result is illustratedin FIG. 5. As can be seen in FIG. 5, the obtained boiling curve issmooth in the boiling range from 130° C. to 370° C. A smooth boilingpoint distribution, or lack of distinctive steps in such a boiling pointdistribution, is advantageous to achieve suitable product specification(such as Jet A1 or JP8) for use in a jet fuel.

TABLE 2 Process Conditions for Examples 1a, 1b, 2a, 2b, 3a and 3b (Allon a Single Pass Basis without any Gas or Liquid Recycle) Example 1a 1b2a 2b 3a 3b CCC cat. (SAR) A (20) A (20) B (20) B (20) C (20) C (20) HTcat. sulphided sulphided sulphided sulphided sulphided sulphided6Ni—18Mo/Al 6Ni—18Mo/Al 6Ni—18Mo/Al 6Ni—18Mo/Al 6Ni—18Mo/Al 6Ni—18Mo/Alweight ratio 1.95:1 1.95:1 1.87:1 1.87:1 1.59:1 1.59:1 CCC cat.:HT cat.WHSV CCC cat. 0.53 0.53 0.54 0.54 0.61 0.61 (kg liquid feed/kg cat. hr)WHSV HT cat. 1.03 1.03 1.01 1.01 0.97 0.97 (kg liquid feed/kg cat. hr)temperature (° C.) 300 350 300 350 300 350 pressure (MPa) 12 12 12 12 1212 Hydrogen to 582 582 557 557 622 622 feed ratio (N1 H2/kg feed)

TABLE 3 Product Characteristics for the Liquid Hydrocarbon Product inExamples 1a, 1b, 2a, 2b, 3a and 3b Example 1a 1b 2a 2b 3a 3b oxygencontent of 3.0 1.5 2.3 0.85 <1.0 0.5 the liquid hydrocarbon product (wt%) smooth boiling 140 140 140 140 140 140 above (° C.) 140° C.-370° C.15 23 15 21 17 23 boiling range fraction* (wt % based on weight of mixedketone feed) C5-140° C. boiling 55 48 53.5 47 53 48.5 range fraction*(wt % based on weight of mixed ketone feed) *boiling fractions are basedon ASTM D2887 SIMDIS method.

Example 4: Properties of the Liquid Hydrocarbon Product

This example illustrates the ability to alter the properties of a liquidhydrocarbon product produced, by altering the strength of hydrogenationfunction in a process as illustrated in FIG. 2. In a first variation ofthe process as illustrated in FIG. 2, a carbon-carbon coupling catalystwith high hydrogenation activity, namely a nickel-exchanged mordenitezeolite catalyst containing about 1.5 wt % nickel (carbon-carboncoupling catalyst A), was used as the top catalyst in a stacked bed andsubjected to sulphurization. A high activity sulphided hydrotreatmentcatalyst containing about 18 wt % molybdenum, about 5 wt % nickel andabout 3 wt % phosphor on an alumina support was used as a bottomcatalyst in the same stacked bed, with the volume ratio of carbon-carboncoupling catalyst to hydrotreating catalyst being 1.5:1. The overallWHSV was 0.33 (kg liquid feed/lit cat·hr). Average catalyst bedtemperature was 360° C. and reactor pressure was about 12 MPa. A mixedketone feed as illustrated in table 1 was contacted with the catalysts.The hydrocarbon liquid product produced from a mixed ketone feed havingcomposition as shown in Table 1 was separated from the aqueous layer,and distilled following the ASTM D2892 distillation method. The 140° C.to 250° C. boiling range fraction from this distillation, whichrepresents a kerosene or jet fuel boiling range fraction of thehydrocarbon liquid, was analyzed for density and aromatics. This 140° C.to 250° C. boiling range fraction was found to have a density of 0.77g/mL, and an aromatic content of about 11.5 wt % following the IP 391measurement method. Nearly all aromatics were monoaromatics, with lessthan 0.2% polyaromatics.

In a second variation of the process as illustrated in FIG. 2, acarbon-carbon coupling catalyst with a lower hydrogenation activity,namely a sulphided molybdenum-exchanged zeolite Beta catalyst asprepared in example 5 (carbon-carbon coupling catalyst D), was used incombination with a sulphided hydrotreating catalyst having a lowerhydrogenation activity comprising about 14 wt % molybdenum and about 3wt % cobalt on an alumina support, with the volume ratio ofcarbon-carbon coupling catalyst to hydrotreating catalyst of 4.7:1. Thelower hydrogenation activity of both coupling and hydrotreatingcatalysts resulted in a hydrocarbon liquid product having a higheraromatic content under comparable operating conditions: The overall WHSVwas 0.3 (kg liquid feed/lit cat·hr); Average catalyst bed temperaturewas 360° C.; and reactor pressure was about 12 MPa. Again a mixed ketonefeed as shown in table 1 was contacted with the catalysts. Thehydrocarbon liquid product produced was separated from the aqueouslayer, and distilled following the ASTM D2892 distillation method. The140° C. to 250° C. boiling range fraction had a total aromatic contentof about 19.5 wt %, out of which polyaromatics were about 5.5 wt %. Thedensity of the liquid was higher than the first variation, at 0.795g/mL. Thus, it is possible to alter density and aromatic content ofhydrocarbon liquid product by altering the strength of hydrogenationfunction on the catalyst.

Example 5: Long Term Operation of a Process for the Conversion C3-C12Ketones with the Help of a Sulphided Molybdenum-Exchanged Zeolite BetaCatalyst (Carbon-Carbon Coupling Catalyst D

A molybdenum-exchanged zeolite Beta catalyst was prepared as follows: A0.143 molar (mol/liter) solution of ammonium heptamolybdate tetrahydrate(equivalent to a molybdenum metal concentration of 1 Mol per liter) inwater was prepared. The pH of this solution was adjusted to 6.0 usingammonium hydroxide. Zeolite Beta powder having a silica to alumina molarratio (SiO₂/Al₂O₃ molar ratio) of approximately 20 in ammonium form andhaving a particle size distribution ranging from about 0.1 micrometer toabout 5 micrometer was provided. A slurry of this powder in the ammoniumheptamolybdate solution was prepared with a ratio of 10 mL of ammoniumheptamolybdate solution per gram of zeolite powder to effect ionexchange. The slurry was heated to 95° C. under refluxing and wasmaintained at that temperature for a period of 1 hour allowing amolybdenum-exchanged zeolite Beta powder to be produced. After 1 hour,refluxing was stopped and the slurry was allowed to cool to about 50° C.and filtered. The filter cake containing the molybdenum-exchangedzeolite Beta powder was washed with water to remove any free molybdenumfrom the powder. The molybdenum-exchanged zeolite Beta powder was thendried at room temperature for about 16 hours. Subsequently it was driedat 130° C. for about 16 hours. The molybdenum-exchanged zeolite Beta wasthen calcined in air at 500° C. for 2 hours. The calcinedmolybdenum-exchanged zeolite Beta powder was shaped into extrudatesusing CATAPAL-D boehmite alumina (CATAPAL is a trademark, CATAPAL-Dboehmite alumina is commercially obtainable from Sasol) as the binder.The weight ratio of zeolite powder to alumina in the extrudates was80:20, corresponding to about 80 wt % of molybdenum-exchanged zeoliteBeta in the extrudates. The extrudates were re-calcined in air at 500°C. for 2 hours to prepare a molybdenum exchanged zeolite Beta catalyst.The prepared molbydenum-exchanged zeolite Beta catalyst containedapproximately 2.5 wt % Molybdenum on the basis of the total weight ofthe calcined catalyst (carbon-carbon coupling catalyst D).

The molybdenum-exchanged zeolite Beta catalyst (carbon-carbon couplingcatalyst D) was used as a carbon-carbon coupling catalyst in a stackedbed configuration with a cobalt-molybdenum hydrotreatment catalystcomprising about 14 wt % molybdenum and about 3 wt % cobalt on analumina support. The stacked bed consisted of a top bed containing thecarbon-carbon coupling catalyst D (i.e. the molybdenum-exchanged zeoliteBeta catalyst) and a bottom bed containing the hydrotreatment catalyst(i.e. the catalyst comprising cobalt and molybdenum on an aluminacarrier). The volume ratio between the carbon-carbon coupling catalyst Dand the hydrotreating catalyst was 82.5:17.5. The top catalyst bed waslocated upstream of the bottom catalyst bed.

After loading the catalysts into the stacked bed, both catalysts weresubjected to a sulfidation treatment. The sulfidation was carried out byusing a straight-run gasoil spiked with dimethyl disulfide (DMDS) toobtain an activation feed having 2.5 wt % elemental sulfur. Afterestablishing a hydrogen flow of 250 Nl H₂/(lit cat·hr) and an activationfeed flow of 0.50 lit liquid/(lit cat·hr), the reactor temperature wasincreased to 360° C. and held at that temperature until H₂S levels inthe off-gas stabilized. If so desired sulfidation of the catalyst canalso be accomplished using gas-phase sulfidation with 5 vol % H₂S/H₂mixture as the sulfiding medium, but this was not applied for thisexperiment.

To illustrate the stability of the sulphided molybdenum-exchangedzeolite Beta catalyst in the process of the invention, a long-term testwas conducted where, in the presence of hydrogen, a mixed ketone feedhaving the composition as shown in table 1 was contacted with thecarbon-carbon coupling catalyst (i.e. the sulphided molybdenum-exchangedzeolite Beta catalyst) in the top (first) catalyst bed and thehydrotreatment catalyst (i.e. the sulphided catalyst comprising cobaltand molybdenum on an alumina carrier) in the bottom (second) catalystbed in the reactor as illustrated in FIG. 2. The mixed ketone feed wasspiked with dimethyldisulphide (DMDS) such that it contained about 0.1wt % (1000 ppmw) sulphur.

A step-wise program was applied where the reactor temperature wasincreased from 250° C. to 360° C. in steps while holding at each stepfor several days. The temperature was then reduced in steps to 320° C.The detailed conditions for the step-wise program are listed in table 4.During the temperature ramp-up, at 320° C. and a hydrogen partialpressure of 12 MegaPascal (condition C in table 4), a middle distillateproduct yield (defined as that part of the product boiling between 140°C. and 370° C. based on ASTM D2887) of 14-15 wt % was obtained afterabout 320 hours on stream. During the ramp-down, at the same temperature(condition G in table 4), after >700 hours on stream, middle distillateyield remained stable at 14-15 wt % even though a lower pressure of 6MegaPascal was applied. Thus, the sulphided molybdenum-exchanged zeoliteBeta catalyst continued to act as a carbon-carbon coupling catalystafter an extended time on stream.

Thus, the use of a catalyst as claimed in the current invention incombination with hydrogen partial pressures of more than 1.0 MegaPascal,more preferably more than 2.0 MegaPascal provides extended stabilityagainst deactivation due to coke formation and/or catalyst poisoning.

TABLE 4 Detailed Conditions for the Step-Wise Program in Example 5Hydrogen to Hydrogen liquid Temper- partial WHSV (kg ratio aturepressure liq/lit (Nl H₂/kg Product Condition (° C.) (MPa) cat.hr) feed)examined A 250 12.0 0.28 750 B 280 12.0 0.28 750 C 320 12.0 0.28 750 x D360 12.0 0.28 750 E 360 8.0 0.28 750 F 360 4.0 0.28 750 G 320 5.8 0.28750 x

Example 6: Conversion of a Mixed Feed of Ketones in a Stacked BedContaining a Nickel-Impregnated Mordenite Zeolite Catalyst(Carbon-Carbon Coupling Catalyst E) and a Hydrotreatment Catalyst

Extrudates were prepared by mixing mordenite zeolite (obtained fromZeolyst International), having a SiO2 to Al2O3 molar ratio ofapproximately 20, with CATAPAL-D boehmite alumina (CATAPAL is atrademark, CATAPAL-D boehmite alumina is commercially obtainable fromSasol) as a binder in a ratio of 20 wt % alumina to 80 wt % mordenitezeolite. The extrudates containing 80 wt % mordenite zeolite bound with20% CATAPAL-D boehmite alumina were impregnated with a Nickel (II)nitrate solution to obtain a nickel exchanged mordenite zeolite with anickel loading of 0.9 wt %. The Nickel(II) nitrate was used as thenickel precursor. The impregnated extrudates were calcined at 500° C. toobtain a nickel-impregnated mordenite zeolite catalyst (carbon-carboncoupling catalyst E).

The prepared nickel-impregnated mordenite zeolite catalyst(carbon-carbon coupling catalyst E) was loaded into a stacked bed systemas a top bed catalyst. The bottom catalyst bed of the stacked bed systemcontained a nickel-molybdenum hydrotreating catalyst containing about 18wt % molybdenum, about 5 wt % nickel and about 3 wt % phosphor on analumina support (herein also referred to as 5Ni-18Mo/Al). The volumeratio of carbon-carbon coupling catalyst to hydrotreating catalyst was4:1, and the corresponding weight ratio was 2.7:1.

Subsequently the loaded carbon-carbon coupling catalyst E and thenickel-molybdenum hydrotreating catalyst were subjected to a liquidphase sulfidation treatment using a sulfidation feed. The sulfidationfeed was a gasoil spiked with dimethyldisulphide (DMDS) to obtain asulfur content of 2.5 wt % in the feed. Sulfidation was carried byflowing hydrogen and the sulfidation feed over the stacked bed catalystsystem at a temperature of 320° C. and a pressure of 2.5 MegaPascal fora period of 4 hours.

After sulphiding of the catalysts, a feed containing a mixture ofketones having predominantly 3 to 10 carbon atoms as illustrated intable 5 was contacted with the catalysts at the conditions summarized intable 6 for example 6.

The feed containing the mixture of ketones was derived from thefermentation of food waste.

TABLE 5 Mixed Ketone Feed Used in Examples 6, 7 and 8 Component Wt %Acetone 12.8 2-Butanone 11.3 2-Pentanone 17.4 Methyl isobutyl ketone 1.62-Hexanone 6.9 4-Heptanone 1.1 3-Heptanone 0.9 2-Heptanone 10.84-Octanone 1.3 3-Octanone 2.0 2-Octanone 2.6 4-Nonanone 2.2 3-Nonanone0.5 2-Nonanone 1.00 3-Decanone 0.23

The sulfur content of this feed was about 500 ppmw. The feed was spikedwith dimethyldisulphide (DMDS) to increase its sulfur content to about1100 ppmw. The feed also had a total nitrogen content of about 1700ppmw, out of which about 410 ppmw was basic nitrogen. The elementaloxygen content of the feed was measured to be about 20%.

The processing of the feed was carried out over the stacked bed catalystsystem at an average bed temperature of 341° C. and a reactor pressureof 12 MegaPascal. A hydrogen to liquid feed ratio of 1952 Nl H2/kg feedwas used, and the space velocity with reference to the carbon-carboncoupling catalyst was 0.52 kg liquid feed/(kg catalyst·hr). The overallspace velocity was 0.38 kg liquid feed/(kg catalyst·hr).

A two-layered product comprising an aqueous layer and an organic(hydrocarbon) layer was obtained.

The liquid hydrocarbon product (in this case consisting of the organichydrocarbon layer) was separated from the reactor effluent. Productcharacteristics for the liquid hydrocarbon product obtained are listedin table 7 for example 6. The hydrocarbon liquid was analyzed for itsboiling range using SIMDIS (ASTM D2887 method). The liquid hydrocarbonproduct fraction boiling between 140° C. and 370° C. may be suitable foruse in a jet fuel and/or diesel after further distillation. The liquidhydrocarbon product fraction boiling between C5-140° C. may be suitableas a hydrocarbon boiling in the gasoline range.

Example 7: Conversion of a Mixed Feed of Ketones in a Stacked BedContaining a Co-Mulled Nickel-Zeolite Beta Catalyst (Carbon-CarbonCoupling Catalyst F) and a Hydrotreatment Catalyst

A carbon-carbon coupling catalyst was prepared by co-mulling as follows.Zeolite Beta powder in an ammonium form having an SiO2 to Al2O3 molarratio of 25 was co-mulled with PURAL SB boehmite alumina (PURAL is atrademark, PURAL-SB boehmite alumina is commercially obtainable fromSasol) as a binder. The weight ratio of zeolite beta powder to thealumina binder was 4:1. During mulling, a nickel nitrate solution wasadded to achieve a nickel loading of 2 wt % on the final extrudate(corresponding to a 2.54 wt % nickeloxide (NiO) loading). The co-mulledmaterial was extruded and the extrudates were calcined at a temperatureof 500° C. to prepare the co-mulled nickel-zeolite beta catalyst(carbon-carbon coupling catalyst F).

The prepared co-mulled nickel-zeolite beta catalyst (carbon-carboncoupling catalyst F) was loaded into a stacked bed system as a top bedcatalyst. The bottom catalyst bed of the stacked bed system contained anickel-molybdenum hydrotreating catalyst containing about 18 wt %molybdenum, about 5 wt % nickel and about 3 wt % phosphor on an aluminasupport. The weight ration of carbon-carbon coupling catalyst F tonickel-molybdenum hydrotreating catalyst was 1.82:1.

The catalyst system was subjected to a liquid phase sulfidationtreatment using a sulfidation feed. The sulfidation feed was a gasoilspiked with dimethyldisulphide (DMDS) to obtain a sulfur content of 2.5wt % in the feed. Sulfidation was carried by flowing hydrogen and thesulfidation feed over the stacked bed catalyst system at a temperatureof 320° C. and a pressure of 2.5 MegaPascal for a period of 4 hours.Both catalyst systems were subjected to identical sulfidation treatment.

A mixed ketone feed as illustrated in table 5 was processed over thecombination of carbon-carbon coupling catalyst F and nickel-molybdenumhydrotreatment catalyst at a temperature of 360° C. The reactor having astacked bed catalyst configuration with the carbon-carbon couplingcatalyst F at the top, and the hydrotreating catalyst at the bottom, wasloaded with 510 mg of the carbon-carbon coupling catalyst and 280 mg ofthe hydrotreating catalyst. The mixed ketone feed flow to this reactorwas 304 mg/hr, resulting in a weight hourly space velocity, based oncarbon-carbon coupling catalyst, of 0.60 kg feed/(kg catalyst·hr), whilethat based on the hydrotreating catalyst was 1.08 kg feed/(kgcatalyst·hr). Overall weight hourly space velocity for the stacked bedsystem was 0.39 kg feed/(kg total catalyst·hr).

The liquid hydrocarbon product was separated from the reactor effluent.Product characteristics for the liquid hydrocarbon product obtained arelisted in table 7 for example 7.

Comparative Example 8: Conversion of a Mixed Feed of Ketones in CatalystBed Containing Only a Hydrotreatment Catalyst

1344 milligram (mg) of the hydrotreatment catalyst used in example 7 wassubjected to a liquid phase sulfidation treatment using a sulfidationfeed. The sulfidation feed was a gasoil spiked with dimethyldisulphide(DMDS) to obtain a sulfur content of 2.5 wt % in the feed. Sulfidationwas carried by flowing hydrogen and the sulfidation feed over thecatalyst at a temperature of 320° C. and a pressure of 2.5 MegaPascalfor a period of 4 hours.

A mixed ketone feed as illustrated in table 5 was processed over thehydrotreatment catalyst at a temperature of 360° C. The mixed ketonefeed flow was 330 mg/hr. Thus, in this example the reactor was operatedwith a weight hourly space velocity of 0.25 kg feed/(kg catalyst·hr).

The liquid hydrocarbon product (in this case consisting of the organichydrocarbon layer) was separated from the reactor effluent. Productcharacteristics for the liquid hydrocarbon product obtained are listedin table 7 for comparative example 8.

As illustrated by example 7 and comparative example 8, the presence of acarbon-carbon coupling agent may increase the yield of middle distillateboiling hydrocarbons by about 100%.

Example 6 even shows an improvement in yield of middle distillateboiling hydrocarbons of about 170%, as compared to comparative example8.

TABLE 6 Process Conditions for Examples 6, 7 and Comparative Example 8(All on a Single Pass Basis without any Gas or Liquid Recycle) Example 67 8 (comparative) CCC cat. (SAR) E (20) F not applicable weight of CCCcat. — 510 not applicable (mg) HT cat. sulfided sulfided sulfided5Ni—18Mo/Al 5Ni—18Mo/Al 5Ni—18Mo/Al weight of HT cat. (mg) — 280 1344weight ratio CCC cat. 2.7:1 1.82:1 not applicable to HT cat. WHSV CCCcat. (kg 0.52 0.60 not applicable liquid feed/kg cat.hr) WHSV HT cat.(kg 1.40 1.07 0.25 liquid feed/kg cat.hr) temperature (° C.) 340 360 360pressure (MegaPascal) 12 2.5 2.5 Hydrogen to mixed 1952 2332 2126 ketonefeed ratio (Nl H2/kg feed) “CCC cat.” refers to the “carbon-carboncoupling catalyst”; and the abbreviation “HT cat.” refers to the“hydrotreatment catalyst”.

TABLE 7 Product Characteristics for the Liquid Hydrocarbon Product inExamples 6, 7 and Comparative Example 8 Example 6 7 8 (comparative)Oxygen content of the <0.2  0.23 0.1  liquid hydrocarbon product (wt %)smooth boiling above 150 — — (° C.) 140° C.-370° C. boiling 21 15.517.75 range fraction* (wt % based on weight of ketone feed) C5-140° C.boiling range 47 — — fraction* (wt % based on weight of ketone feed)*boiling fractions are based on ASTM D2887 SIMDIS method.

That which is claimed is:
 1. A process for converting one or more C3-C12oxygenates comprising: contacting a feed, which feed comprises one ormore C3-C12 oxygenates, with hydrogen at a hydrogen partial pressure ofmore than 1.0 MegaPascal in the presence of a sulphided carbon-carboncoupling catalyst; wherein the carbon-carbon coupling catalyst comprisesat least 60 wt % of a zeolite and in the range from at least 0.1 wt % toat most 10 wt % of a hydrogenation metal, based on the total weight ofthe carbon-carbon coupling catalyst; and wherein the zeolite comprises10-membered and/or 12-membered ring channels and a Silica to Aluminamolar Ratio (SAR) in the range from 10 to
 300. 2. The process accordingto claim 1 wherein the carbon-carbon coupling catalyst comprises in therange from at least 0.5 wt % to at most 5 wt % of a hydrogenation metal,based on the total weight of the carbon-carbon coupling catalyst.
 3. Theprocess according to claim 1 wherein the feed is contacted with thesulphided carbon-carbon coupling catalyst at a temperature in the rangefrom at least 250° C. to at most 450° C.
 4. The process according toclaim 1 wherein the feed comprises sulphur in a concentration in therange from at least 150 ppmw to at most 2000 ppmw.
 5. The processaccording to claim 1 wherein the feed comprises nitrogen in aconcentration in the range from at least 300 ppmw to at most 5000 ppmw.6. The process according to claim 1 wherein a conversion product isproduced, which conversion product is subsequently contacted with ahydrotreating catalyst and/or a hydroisomerization catalyst.
 7. Theprocess according to claim 6 wherein the sulphided carbon-carboncoupling catalyst and the hydrotreating catalyst and/orhydroisomerization catalyst are combined in a stacked bed configuration,where the sulphided carbon-carbon coupling catalyst is located upstreamof the hydrotreating catalyst and/or hydroisomerization catalyst.
 8. Theprocess according to claim 6 wherein the weight ratio of sulphidedcarbon-carbon coupling catalyst to hydrotreating catalyst and/or ahydroisomerization catalyst is from 1:1 to 4:1.
 9. The process accordingto claim 1 wherein further a C1-C3 hydrocarbon product is produced,which C1-C3 hydrocarbon product is converted in a steam methane reformerto produce hydrogen.
 10. The process according to claim 9 wherein theproduced hydrogen is recycled to the process.
 11. The process accordingto claim 1 wherein a middle distillate boiling product is produced.